Edge X-ray Magnetic Circular Dichroism Research Articles

3d and 5d electronic structures and orbital hybridization in Ba- and Ca-doped La2CoIrO6 double perovskites

Here we present a detailed investigation of the Co and Ir local electronic structures in ${\mathrm{La}}_{1.5}{A}_{0.5}{\mathrm{CoIrO}}_{6}$ ($A=\mathrm{Ba}$, Ca) compounds in order to unravel the orbital hybridization mechanism in these CoIr-based double perovskites. Our results of x-ray powder diffraction, ac and dc magnetization, Co and Ir ${L}_{2,3}$-edge and Co $K$-edge x-ray absorption spectroscopy and x-ray magnetic circular dichroism suggest a competition between magnetic interactions. A dominant antiferromagnetic coupling is found to be responsible for the ferrimagnetic behavior observed for $A=\mathrm{Ca}$ below $\ensuremath{\sim}96\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, the competing magnetic phases, and the cationic disorder in this compound giving rise to a spin-glass state at low temperatures. For the $A=\mathrm{Ba}$, on the other hand, there is no evidence of long-range order down to its spin-glass transition temperature. The remarkably different magnetic properties observed between these two compounds are discussed in terms of the structural distortion that alters the strength of the Co-Ir couplings, with a relevant role played by the Co $3d\phantom{\rule{4pt}{0ex}}{e}_{g}--\mathrm{Ir} 5d\phantom{\rule{4pt}{0ex}}{j}_{\mathrm{eff}}=1/2$ hybridization.

Synchrotron X-ray spectroscopic study of the antiferromagnetic-ferromagnetic transition in Ni-doped FeRh epitaxial thin films

We investigate the change of magnetism and electronic structure across the antiferromagnetic (AFM) -ferromagnetic (FM) transition of Ni-doped FeRh epitaxial thin films by x-ray magnetic circular dichroism (XMCD) and hard x-ray photoemission spectroscopy (HAXPES). The Rh L edge XMCD results indicate that the remnant FM phase at low temperature possesses smaller Rh moment than the normal FM phase which can undergo AFM-FM transition. The HAXPES results confirm an increase of Rh 4d density of state at the Fermi level and a possible “well-screened” state at the Ni 2p photoemission in the FM phase. FM fluctuation of the inter-site Fe-Fe exchange coupling within the AFM phase can be interpreted from the temperature dependence of the Fe 2p HAXPES results.

Single-domain perpendicular magnetization induced by the coherent O 2p -Ru 4d hybridized state in an ultra-high-quality SrRuO3 film

We investigated the Ru $4d$ and O $2p$ electronic structure and magnetic properties of an ultrahigh-quality $\mathrm{SrRu}{\mathrm{O}}_{3}$ film on $\mathrm{SrTi}{\mathrm{O}}_{3}$ grown by machine-learning assisted molecular-beam epitaxy. The high itinerancy and long quantum lifetimes of the quasiparticles in the Ru $4d$ ${t}_{2g}$-O $2p$ hybridized valence band are confirmed by observing the prominent well-screened peak in the Ru $3d$ core-level photoemission spectrum, the coherent peak near the Fermi energy in the valence-band spectrum, and quantum oscillations in the resistivity. The element-specific magnetic properties and the hybridization between the Ru $4d$ and O $2p$ orbitals were characterized by Ru ${M}_{2,3}$-edge and O $K$-edge soft x-ray absorption spectroscopy and x-ray magnetic circular dichroism measurements. The ultrahigh-quality $\mathrm{SrRu}{\mathrm{O}}_{3}$ film with the residual resistivity ratio of 86 shows the large orbital magnetic moment of oxygen ions induced by the strong orbital hybridization of the O $2p$ states with the spin-polarized Ru $4d$ ${t}_{2g}$ states. The film also shows single-domain perpendicular magnetization with an almost ideal remanent magnetization ratio of 0.97. These results provide detailed insights into the relevance between orbital hybridization and the perpendicular magnetic anisotropy in $\mathrm{SrRu}{\mathrm{O}}_{3}/\mathrm{SrTi}{\mathrm{O}}_{3}$ systems.

A cookbook for the investigation of coordination polymers by transition metal K-edge XMCD.

In order to disentangle the physical effects at the origin of transition metal K-edge X-ray magnetic circular dichroism (XMCD) in coordination polymers and quantify small structural distortions from the intensity of these signals, a systematic investigation of Prussian blue analogs as model compounds is being conducted. Here the effects of the temperature and of the external magnetic field are tackled; none of these external parameters modify the shape of the XMCD signal but they both critically modify its intensity. The optimized experimental conditions, as well as a reliable and robust normalization procedure, could thus be determined for the study of the intrinsic parameters. Through an extended discussion on measurements on other XMCD-dedicated beamlines and for other coordination compounds, we finally provide new transition metal K-edge XMCD users with useful information to initiate and successfully carry out their projects.

Influence of Fe doping on the Yb valence state and the magnetic structures in HoFe6Sn6-type YbMn6−yFeySn6 alloys (y ≤ 1.00)

We determine the magnetic structures of HoFe6Sn6-type (Immm) YbMn6−yFeySn6 alloys (y=0.25, 0.50, 0.75 and 1.00) from powder neutron diffraction experiments. The valence state and local magnetism of Yb are investigated using X-ray Near Edge Spectroscopy (XANES) and X-ray Magnetic Circular Dichroism (XMCD) at the Yb L3 edge. The mean Yb valence decreases upon Fe doping (from υ~2.66 down to υ~2.46) and there is no 4f Yb magnetism throughout the series. The Fe for Mn substitution leads to change in the spins arrangement of the 3d sublattice by reinforcing antiferromagnetic exchange interactions without significant change in T=Mn/Fe moment magnitude (m~2.35 µB). The ground state of the alloy with y=0.25 is ferromagnetic whilst Fe richer alloys are helimagnets with wave-vector k=0, qy, 0. The turn-angle increase upon Fe doping manifests by a mitigation of the Yb L3 dichroic effect, solely due to hybridization between its 5d states and the self-polarized 3d states of T.

Crystal Orbital Overlap Population and X-ray Absorption Spectroscopy.

We present an extension of an ab initio numerical tool calculating X-ray absorption spectroscopies and crystal orbital overlap populations at the same time. Density functional theory is used to calculate the electronic structure in both occupied (valence to core X-ray emission spectroscopy) and nonoccupied states (i.e., X-ray absorption near the edge structure and X-ray magnetic circular dichroism) and to evaluate the orbital overlap typifying the covalency between neighboring atoms. We show how the different features in the experimental spectra can be correlated to the chemical bonds around the absorbing atoms in several examples including acrylonitrile molecules, rutile TiO2, Li2RuO3 high-energy density cathode, ZnO, and anti-ferromagnetic V2O3.

Electronic structure investigation of GdNi using x-ray absorption, magnetic circular dichroism, and hard x-ray photoemission spectroscopy

GdNi is a ferrimagnetic material with a Curie temperature Tc = 69 K which exhibits a large magnetocaloric effect, making it useful for magnetic refrigerator applications. We investigate the electronic structure of GdNi by carrying out x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) at T = 25 K in the ferrimagnetic phase. We analyze the Gd M$_{4,5}$-edge ($3d$ - $4f$) and Ni L$_{2,3}$-edge ($2p$ - $3d$) spectra using atomic multiplet and cluster model calculations, respectively. The atomic multiplet calculation for Gd M$_{4,5}$-edge XAS indicates that Gd is trivalent in GdNi, consistent with localized $4f$ states. On the other hand, a model cluster calculation for Ni L$_{2,3}$-edge XAS shows that Ni is effectively divalent in GdNi and strongly hybridized with nearest neighbour Gd states, resulting in a $d$-electron count of 8.57. The Gd M$_{4,5}$-edge XMCD spectrum is consistent with a ground state configuration of S = 7/2 and L=0. The Ni L$_{2,3}$-edge XMCD results indicate that the antiferromagnetically aligned Ni moments exhibit a small but finite magnetic moment ( $m_{tot}$ $\sim$ 0.12 $\mu_B$ ) with the ratio $m_{o}/m_{s}$ $\sim$ 0.11. Valence band hard x-ray photoemission spectroscopy shows Ni $3d$ features at the Fermi level, confirming a partially filled $3d$ band, while the Gd $4f$ states are at high binding energies away from the Fermi level. The results indicate that the Ni $3d$ band is not fully occupied and contradicts the charge-transfer model for rare-earth based alloys. The obtained electronic parameters indicate that GdNi is a strongly correlated charge transfer metal with the Ni on-site Coulomb energy being much larger than the effective charge-transfer energy between the Ni $3d$ and Gd $4f$ states.

Growth-sequence-dependent interface magnetism of SrIrO3–La0.7Sr0.3MnO3 bilayers

Bilayers of the oxide 3d ferromagnet La0.7Sr0.3MnO3 (LSMO) and the 5d paramagnet SrIrO3 (SIO) with large spin–orbit coupling (SOC) have been investigated regarding the impact of interfacial SOC on magnetic order. For the growth sequence of LSMO on SIO, ferromagnetism is strongly altered and large out-of-plane-canted anisotropy associated with lacking magnetic saturation up to 4 T has been observed. Thin bilayer films have been grown coherently in both growth sequences on SrTiO3 (001) by pulsed laser deposition and structurally characterized by scanning transmission electron microscopy and x-ray diffraction. Measurements of magnetization and field-dependent Mn L2,3 edge x-ray magnetic circular dichroism reveal changes of the LSMO magnetic order, which are strong in LSMO on SIO and weak in LSMO underneath SIO. We attribute the impact of the growth sequence to the interfacial lattice structure, which is known to influence the interfacial magnetic coupling governed by MnO6 octahedral rotations and/or distortions.

Pressure-induced first-order magnetic phase transition and Yb ordered moment in YbCu2Si2

We report on high-pressure x-ray absorption near edge structure and x-ray magnetic circular dichroism (XMCD) measurements at the Yb ${L}_{3}$ edge on ${\mathrm{YbCu}}_{2}{\mathrm{Si}}_{2}$. This intermetallic is a well-known intermediate valence compound which shows a pressure-induced paramagnetic-ferromagnetic phase transition at about 8 GPa. The pressure dependence of the Yb magnetization has been determined by following the evolution with pressure of the maximum of the dichroic signal at the energy corresponding to the electric quadrupole ($2{p}_{3/2}\ensuremath{-}4f$) transitions. The observed XMCD deduced magnetization curves confirm the ferromagnetic nature of the high-pressure phase as well as the first-order nature of the transition. The Yb ordered moment deduced from XMCD which amounts to about $1.25{\ensuremath{\mu}}_{B}$ at 8.7 GPa and 2.7 K is in very good agreement with the one estimated by M\"ossbauer spectroscopy for the magnetically ordered component of the spectra. This observation indicates that the paramagnetic and ferromagnetic phases coexist only in a narrow pressure range in our XMCD experiment. This is not the case for the M\"ossbauer measurements, which show that the paramagnetic component vanishes only at 20 GPa. Our results clarify the existing discrepancy with dc magnetization measurements that reported values of the Yb moment more than two times smaller. We propose that these apparent contradictory results are due to different experimental conditions which influence the range of coexistence of the paramagnetic and ferromagnetic phases, as found in many similar situations and frequently addressed in the literature.

Europium Cyclooctatetraene Nanowire Carpets: A Low-Dimensional, Organometallic, and Ferromagnetic Insulator.

We investigate the magnetic and electronic properties of europium cyclooctatetraene (EuCot) nanowires by means of low-temperature X-ray magnetic circular dichroism (XMCD) and scanning tunneling microscopy (STM) and spectroscopy (STS). The EuCot nanowires are prepared in situ on a graphene surface. STS measurements identify EuCot as an insulator with a minority band gap of 2.3 eV. By means of Eu M5,4 edge XMCD, orbital and spin magnetic moments of (-0.1 ± 0.3)μB and (+7.0 ± 0.6)μB, respectively, were determined. Field-dependent measurements of the XMCD signal at the Eu M5 edge show hysteresis for grazing X-ray incidence at 5 K, thus confirming EuCot as a ferromagnetic material. Our density functional theory calculations reproduce the experimentally observed minority band gap. Modeling the experimental results theoretically, we find that the effective interatomic exchange interaction between Eu atoms is on the order of millielectronvolts, that magnetocrystalline anisotropy energy is roughly half as big, and that dipolar energy is approximately ten times lower.

Determination of the ground state of an Au-supported FePc film based on the interpretation of Fe K - and L -edge x-ray magnetic circular dichroism measurements

We determine the magnetic ground state of the FePc molecule on Au-supported thin films based on the observed values of orbital anisotropy and spectroscopic x-ray magnetic circular dichroism (XMCD) measurements at the Fe $K$ and $L$ edges. Starting from ab initio molecular orbital multiplet calculations for the isolated molecule, we diagonalize the spin-orbit interaction in the subspace spanned by the three lowest spin triplet states of ${}^{3}{A}_{2g}$ and ${}^{3}{E}_{g}$ symmetry in the presence of a saturating magnetic field at a polar angle $\ensuremath{\theta}$ with respect to the normal to the plane of the film, plus an external perturbation representing the effect of the molecules in the stack on the FePc molecule under consideration. We find that the orbital moment of the ground state strongly depends on the magnetic field direction in agreement with the sum rule analysis of the ${L}_{23}$-edge XMCD data. We calculate integrals over the XMCD spectra at the Fe $K$ and ${L}_{23}$ edges as used in the sum rules and explicitly show that they agree with the expectation values of the orbital moment and effective spin moment of the ground state. On the basis of this analysis, we can rule out alternative candidates proposed in the literature.

Dzyaloshinskii-Moriya interaction in α−Fe2O3 measured by magnetic circular dichroism in resonant inelastic soft x-ray scattering

Fe ${L}_{2,3}$-edge x-ray absorption spectra (XAS) and magnetic circular dichroism (MCD) in resonant inelastic x-ray scattering (RIXS) of $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Fe}}_{2}{\mathrm{O}}_{3}$ were measured to identify the electronic structure responsible for its weak ferromagnetism caused by the Dzyaloshinskii-Moriya interaction (DMI) at room temperature. In contrast to negligible MCD in XAS, MCD in RIXS (RIXS-MCD) was clearly observed in the $dd$ excitation at 1.8 eV via excitation to charge-transfer states. Furthermore, RIXS-MCD showed a crystal orientation dependence, indicating that the observed RIXS-MCD originated from DMI. The observed RIXS-MCD is well described by ab initio charge-transfer multiplet calculations, revealing that the RIXS-MCD derives from spin flip excitations at delocalized ${e}_{\mathrm{g}}$ orbitals. By the combination of the experiments and calculations, RIXS-MCD has unraveled that the origin of DMI in $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Fe}}_{2}{\mathrm{O}}_{3}$ is the ${e}_{\mathrm{g}}$ orbitals, which are strongly hybridized with the $2p$ orbitals of oxygen atoms. The results demonstrate the importance of RIXS-MCD for identifying the electronic structure related to DMI.

Local Noncentrosymmetric Structure of Bi2Sr2CaCu2O8+y by X-ray Magnetic Circular Dichroism at Cu K-Edge XANES

The two-dimensional Bi2Sr2CaCu2O8+y (Bi2212), the most studied prototype cuprate superconductor, is a lamellar system made of a stack of two-dimensional corrugated CuO2 bilayers separated by Bi2O2+ySr2O2 layers. While the large majority of theories, proposed to interpret unconventional high Tc superconductivity in Bi2Sr2CaCu2O8+y, assume a centrosymmetric tetragonal CuO2 lattice for the [CuO2]Ca[CuO2] bilayer here we report new compelling results providing evidence for local noncentrosymmetric structure at the Cu site. We have measured polarized Cu K-edge XANES (x-ray absorption near edge structure) and the K-edge X-ray magnetic circular dichroism (XMCD) of a Bi2212 single crystal near optimum doping. The Cu K edge XMCD signal was measured at ID12 beamline of ESRF with the k-vector of x-ray beam parallel to c-axis i.e. with the electric field of x-ray beam E//ab, using a 17 T magnetic field parallel to the c-axis of a Bi2212 single crystal. Numerical simulations of the XMCD signal of Bi2212 by multiple scattering theory have shown agreement with the experimental XMCD signal only for the local structure with noncentrosymmetric Bb2b space group of Bi2Sr2CaCu2O8+y.

Effects of spin-orbit interaction in chromium on oxygen K -edge x-ray magnetic circular dichroism spectra in CrO2

We calculate the oxygen $K$-edge x-ray magnetic circular dichroism (XMCD) spectra of ${\mathrm{CrO}}_{2}$ to investigate the origin of light-element XMCD. The XMCD spectra evaluated by using a multiple scattering theory are interpreted in terms of the spin-orbit interaction (SOI) at each atomic site. We find that the SOI at the nearest-neighbor Cr atoms dominantly contributes to the oxygen $K$-edge XMCD. Since it has been speculated that XMCD originates from the spin polarization and the SOI at the x-ray-absorbing atom, the present finding may lead to modification of the previously speculated mechanism underlying $K$-edge XMCD. We also perform calculations with a small ${\mathrm{CrO}}_{2}$ cluster to examine how the O-$p$ and Cr-$d$ states are hybridized and how oxygen atoms acquire orbital angular momentum density. Strong $K$-edge XMCD features reflect the character of the $d$ states of neighboring magnetic atoms and do not directly connect to the orbital magnetic moments of light-element $p$ states.

Sum rule distortions in fluorescence-yield x-ray magnetic circular dichroism

The quantitative analysis of $3d$ transition metal ${\mathrm{L}}_{2,3}$ edge x-ray magnetic circular dichroism (XMCD) spectra and the related sum rules are compared for measurements with electron yield and fluorescence yield detection. Multiplet calculations on divalent ions show that fluorescence yield detected sum rule derived expectation values of ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ show noticeable deviations and detection angle dependence. We show that small deviations of the polarization dependent fluorescent decay values lead to significant deviations in the ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ sum rule values. Fe and Co experimental XMCD spectra of a supported 10 nm ${\mathrm{CoFe}}_{2}{\mathrm{O}}_{4}$ thin film are measured simultaneously by both electron and fluorescence yield. The deviations shown in the experimental data are well explained by the calculations and are shown to mainly depend on the polarization dependent total decay. We conclude that fluorescence yield detected x-ray magnetic circular dichroism is unsuitable for quantitative analysis of the ${\mathrm{L}}_{z}$ and ${\mathrm{S}}_{z}$ sum rule values.

Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase.

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]−/2–), to ferric and ferrous tetrathiolates ([Fe(SR)4]−/2–), to diferric and mixed-valent iron–sulfur complexes [Fe2S2R4]2–/3–. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal–iron–sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems.

XMCD study of the local magnetic and structural properties of microcrystalline NdFeB-based alloys

X-ray Magnetic Circular Dichroism (XMCD) technique was used to investigate local magnetic properties of microcrystalline Nd10.4Zr4.0Fe79.2B6.4 samples, oriented along either easy or hard magnetization direction. The Nd L 2,3 and Fe K edge XMCD spectra were measured at room temperature under a magnetic field of T. A very strong dependence of XMCD spectra on the sample orientation has been observed at the NdL 2,3-edges, whereas the Fe K-edge XMCD spectra are found to be practically isotropic. This result indicates that magnetic anisotropy of NdFeB-based alloys originates from the Nd sublattice. In addition, element selective magnetization curves have been recorded by measuring the intensity of XMCD signals as a function of an applied magnetic field up to T. To find a correlation between local and macroscopic magnetic properties of studied samples we compared these data with magnetization curves, measured by vibrating sample magnetometer up to T. Results are important for understanding the origin of high-coercivity state in NdFeB-based intermetallic compounds.

Pressure effect on the magnetism of the diluted magnetic semiconductor(Ba1−xKx)(Zn1−yMny)2As2with independent spin and charge doping

We used x-ray magnetic circular dichroism (XMCD) to probe the ferromagnetic properties of As $p$-symmetric ($4p$) states in the recently synthesized diluted magnetic semiconductor $(\mathrm{B}{\mathrm{a}}_{1\ensuremath{-}x}{\mathrm{K}}_{x}){(\mathrm{Z}{\mathrm{n}}_{1\ensuremath{-}y}\mathrm{M}{\mathrm{n}}_{y})}_{2}\mathrm{A}{\mathrm{s}}_{2}$ system under ambient- and high-pressure conditions. The As $K$-edge XMCD signal scales with the sample magnetization (dominated by Mn) and scales with the ferromagnetic ordering temperature $T\mathrm{c}$, and hence it is representative of the bulk magnetization. The XMCD intensity gradually decreases upon compression and vanishes at around 25 GPa, indicating quenching of ferromagnetism at this pressure. Transport measurements show a concomitant increase in conductivity with pressure, leading to a nearly metallic state at about the same pressure where magnetic order collapses. High-pressure x-ray diffraction shows an absence of structural transitions to 40 GPa. The results indicate that the mobility of doped holes, probed by both transport and x-ray absorption spectroscopy ($4p$ band broadening), is intimately connected with the mechanism of magnetic ordering in this class of compounds and that its control using external pressure provides an alternative route for tuning the magnetic properties in diluted magnetic semiconductor materials.

Magnetic ordering in magnetic shape memory alloy Ni-Mn-In-Co

Structural and magnetic properties across the martensite-austenite phase transitions in the shape memory alloy Ni-Mn-In-Co are studied using complementary experimental techniques: ferromagnetic resonance, macroscopic magnetization measurements, and x-ray magnetic circular dichroism in the temperature range from 5 to 450 K. Ferromagnetic resonance experiments show coexisting antiferromagnetic and ferromagnetic correlations for the martensite phase and ferromagnetic and paramagnetic correlations in the austenite phase. Magnetization measurements reveal spin-glass-like behavior for $Tl30$ K and Ni and Co $K$-edge x-ray magnetic circular dichroism measurements confirm an assignment of a ferromagnetic resonance line purely to Ni (and Co) for a wide temperature range from 125 to 225 K. Hence a combined analysis of ferromagnetic resonance and x-ray magnetic circular dichroism allows us to attribute particular magnetic resonance signals to individual elemental species in the alloy.

X-ray magnetic circular dichroism study of an orbital ordered state in the spinel-type vanadium oxideAV2O4(A=Mn,Fe)

Spinel-type vanadium oxides ${\mathrm{FeV}}_{2}{\mathrm{O}}_{4}$ and ${\mathrm{MnV}}_{2}{\mathrm{O}}_{4}$ are considered to exhibit different types of ${\mathrm{V}}^{3+}$ orbital order from each other. In order to tackle this issue, the temperature dependence of x-ray absorption spectrum (XAS) and x-ray magnetic circular dichroism (XMCD) spectrum are investigated in both spinel compounds. The application of the sum rule to the obtained V edge XMCD spectra and the comparison with crystal-field multiplet calculations suggest a real orbital ordered state with quenched orbital angular momenta in both ${\mathrm{FeV}}_{2}{\mathrm{O}}_{4}$ and ${\mathrm{MnV}}_{2}{\mathrm{O}}_{4}$. A dissimilarity in XAS spectra between these compounds would originate from a quantitative difference of trigonal distortion.